Edwin b



`E. D. CHAPL|N. SULFURIC ACID NIANUFACTUIIE.

APPLICATION FILED IIIAII.` l0.l |916 Patented Dee. 23, 1919.

EDWIN D. CHAPLIN, 0F NEW YORK, N. Y.

SULFURIC-ACID MANUFACTUBE.

Specification of Letters Patent.

Patented Dec. 23,1919.

Application led Match 1G, 1916.` Serial No. 83,218.

.To all Iwlw/1r it may concern.'

Be 1t known that l, EDWIN D. CHAPLIN,

a citizen ofthe United States, residing in New York, in the county of New York and State of New York, have invented certain new and useful Improvements in Sulfuric- Acid lllanufacture, of which the following is a specication.

rl`l1is invention relates more especially to the manufacture of sulfuric acid (H2S04) in conjunction with sulfur. trioXid (S03), for thereby producing the commercial product commonly designated as firming acid, which may be said to consist of sulfur trionid dissolved in sulfuric acid. A principal object ot my present invention is to furnish an improved process for the continuous and economical production of the firming grade of acid by the aid of a primary process in which and whereby a given quantity of chlorin is continuously employed in a bll closed circuit, for directly coperating with other materials and products in successive stages of the respective processes, as hereinafter more fully explained.

The leading features of the principal process whereby the` lseveral supplies of acidforrning materials, or ingredients, are assembled and incorporated, and subjected to acidformingreactions in the combining chamber, are only incidentally described and are not broadly claimed herein, since those process :improvements are more fully set forth in, and constitute'in part the subject-matter of my copending application Serial No. 74,530, tiled Jan. Q7, 1916, to which reference may be had.

lfor the purposes of this specication, the so called turning grades of sulfuric acid products are herein regarded as being composed of a. quantity of sultur trioXid (S03) which is in a state of combination with water, (H20), while this combination has dissolved therein a further quantity (in the nature of an excess) of the sulfur trioXid. This view appears to be consistent with the recognized phenomenon that when such a sulfu'rcompound is exposed to the atmos-I phere at ordinary temperatures, sulfur trioXid is lost by a kind of evaporation which ultimately reduces the compound from the formula ll2S0,-{S03 to the formula ll2S0,. ln some instances,however, thisl transformation may proceed injftwo ways at the same timefirst by such an evaporation of the said excess, or uncornbined,. sulfur trioxid,

and second, by a concurrent absorption of Water, H20, from the atmosphere. ln this or some analogous manner, some part of said excess S03 will be converted gradually into H'SOM which is wellknown to be a stable compound at ordinary low temperatures. lVhen by such reductions, the said,

excess S03 has been entirely disposed of, the

remalning compound is designated as 100% sulfuric acid, and this on further exposure to moisture will gradually become more and more dilute by absorption of an excess quan tity of Water, which, perhaps, may not be in a state of combination with the sulfur trioxid; but this question is not deemed to be a material one as regards the present invention and application.

ln the accompanying drawings, the figure diagrammatically illustrates,-partly in ver tical section,an arrangement of apparatus adapted for carryingout my improved processes.

As in illustration of the manner in which the acid plant maybe installed in a building, some portions of the apparatus are shown set upon a floor, as B, which in practice is preferably a concrete floor in the lower story of a building which also has an upper door, as l?, upon which other portions of the apparatus may be arranged conveniently for access and supervision by the operators. The apparatus may, in practice, be supplied with pressure gages (not shown) applied in a well-known manner, whereby the attendants may observe the pressures within the several pipes and other members throughout the plant, and thus be enabled to more readily regulate the several supply-controlling valves, and other details. The -hereindescribed improvements in the apparatus, however, arc not claimed herein, but so far as they are of my invention will constitute in part the subject-matter of separate cependingapplications.

eferring to the drawing, this shows the pipe 8 for conducting steam,-preferably somewhat superheated and drm-from. some suitable boiler, as 5, to a tube or ejector member', 8, whichterminates in a nozzle n, and is provided with a regulatingyalve, 9, whereby the steam may be released from a higher pressure in the member 8 to a lower pressure within the-more forward nozzle, n', which communicates with the chamber P through the annular conduit, or throat at t. A similar supply-chamber P", surrounds ]et. y

One of the principal parts of the apparatus illustrated in the drawing, consists of the cmbininglapparatus shown in position above the floor F. This apparatus in the suita ,le arrangement,-not herein shown.

form thereof herein shown, is in certain respects and details, in the nature of an improvement on the similar apparatus which `is shown in my copending application, Serial No. 74530, filed -Jan.y 27, 1916, to which reference may be had. In the present apparatus, however, the details are so arranged as to mix the several materials `in an nnproved manner, but nevertheless, in some instances if desired, the less complex forni of combining apparatus shown in said application No. 74530, may b'e substituted for the purposes of my present processes, for the particular form of said apparatus herein shown.

The chamber P is shown connected by the pipe 2 and through a supply-regulating valve 3, with the interior of a sulfur-burner at 1, and the chamber I is similarly connected through a pipe, 29, (having a supplyregulating valve, 30), with one endl ofV an acid-dissociating retort 20, which may be arranged,-as hereinindicated,-in a position for being. heated by the combustion of the sulfur within the burner 1. The 'steamboiler, 5, may also be arranged for operation lbythe heat from the sulfur-burner either by placing the boiler over said burner (as o gin the drawing), or by some other Throughthe pipe 8, steam is supplied to the combining apparatus; through theipe 2, sulfur dioxid and a carrier gas (S52 and N) are supplied to the chamber P; the pipe 29 supplies to the chamber P from the apparatus 20, chlorin, hydrogen, oxygen and nitrogen, probably related thus: Cl and H2O, (water vapor) and N." The pipes- 2 and 29, therefore, supply nitrogen tothe chambers P and P, respectively, for use as a diluent, or as a neutral carrier gas, during and subsequent to the reaction period, in the combining space 4 and beyond, in the circuit of the apparatus.

AIn the present arrangement of the apparatus, the sulfur-dioxid is first mixed or in- I cor'pn:ated by (or at) the nozzle n, and these materials (with some nitrogen) form a jetstream whichvissues through the nozzle n', for combiningwith the chlorin and associated substances supplied (as already mentioned)' f"riito the principal reaction tube or chamber, at 4. .This 'specific process of the `said successive in'corporations of the `said substance in the way and manner here set forth is not broadly claimed herein, since it is intended to form the subject matter of a separate application.

The combining chamber, 4, is herein indicated as being of a tubular form, but of a relatively short length and terminating in a larger chamber Gr, preferably nearly globular in form and arranged for acting as a mixing chamber. The chamber 4 is also shown provided on the interior thereof with spiral (or helical) ribs, g, arranged for iinparting to the outer portion of the jetstream ofl gases, a whirlin movement as they enter the space G, and t ereby promote a violent mechanical agitation and intermixing of all the gases while the acid-forming ingredients are still'undergoing the normal reactions in the rapidly expanding steam and before the complete dissociation thereof.

From the mixing-space G, the gases, in this instance, are led olf (transversely to the combining space 4), t o a cooling coil, as 40, within a water-tank, T, and terminating in the pipe 31, through which the materials pass to subsequent stages of the cycle of operations or steps, comprised in the processes. Thisl cooling apparatus,or such other suitable apparatus as may be substituted for the particular form and arrangement here indicated`,`may be made of such size and proportions as may be found desirable for effectively coperating with the other portions of the plant.

When the quantities of materials passing through the reaction-spaces 4 and G, are relatively large, naturally some residual quantities of uncoinbined acid-forming ingredients may pass out of the space Gr, mixed with a large proportionof the neutral or non-combining carrier-gas, and for dealing more effectively with such residual quantities, I have herein indicated a secondary mixing apparatus located intermediate to the aforesaid combining apparatus and the cooling apparatus at T. This secondary appafatusmay be arranged in a horizontal manner, (not shown), but the vertically-disposed'arrangementxherein illustrated at D, is deemed tobe the preferable one. Within the tank D, a series( of 'chambers, d, d, of any suitable or requirevd'size and proportions are shown arranged v"with short connecting pipes d of'azrelatively'small diameter. In passing from the combining-space, (whether this be the space G, lor, otherwise), the gases pass through thepperiii'ost "f the pipes d into the uppermostlspace d; 'and in an analogous manner pass-*through'the remaining said pipes 'and spacestofthe ipe 40 of the coil 4Q.- In thus'jprogressinglihrough the 'apparatusja't -D, the` gasesfare alternately subjected: High velocityl in. a contracted stream throng pipes di, and then the stream is expag'ndedl and further intermixed in the lform of a liquid, as

spaces d, thereby producing a very complete incorporation of the constantly decreasing volume of the acid-forming ing 1edients which are mingled With the carrier gas.

The product materials, including the condensed liquids and the gases, pass from the cooling apparatus l, through the pipe 3l and valve 32 into a collection chamber, 50, from which the liquids may be drawn ed from time to time by the discharge pipe and valve at 51. rlhe line 52 may be considered as a normal liquid-level Within the tank or reservoir 50, in which the space above said line serves as a gas-holder for the hydrochloric acid gas, and also for the carriergas. lln the present instance, the accumulated gases ,pass from the holder 50 through pipe 53 to a liquefying compressor lt, (which may be of any suitable and well-known construction), in Which the hydrochloric acid gas becomes compressed into a liquid, and is thence discharged through the pipe 5l into the relatively tall reservoir column M for a gravitational separation of the hydrochloric fluids and vapors from thecarrier-gas, this consisting mainly of nitrogen. p

For separating and disposing of the said carrier-gas, a supplemental apparatus may be conveniently arranged. as follows: A pipe, 55, leading from the top of column M,

enters the bottom of the tank 60 in which a body of Water, 6l, may be suppliedV-preferably by or from a pressure-supply (not shown),-in a Well-known manner. 'llhus the nitrogen or other neutral carrier-gas from pipe 55 is Washed7 of its absorbed acid vapors by the Water 61, which thereby takes up a large portion of such vapors and gradually becomes aqueous hydrochloric acid; when of a desired strengththis acid may be drawn off from time to time through the pipe 62 and more Water supplied to the tan-k 60. The gases entering .the reservoir 60 and not absorbed by the bath or water 61, may be automatically discharged by means of a pressure-controlled reliefvalve, as 65, which should, in practice, be adjusted for automatic operation Whenever the gas-pressure Within the tank 60 and column M rises to a suitable predetermined amount.

lFor supplying the hydrochloric material from the apparatus M to the apparatus at 20, a pipe 56 is shown leading to a valvednozzle device, 57, which also connects by a pipe 58 with some suitable air-supplying pump indicated at M2. A valve, 57', may be arranged for regulating the admission of the hydrochloric acid, (preferably in the herein indicated) from the pipe 56 to the retort Il, and for there mixing such Huid in a spray with the air from said air-supply pump. The air thus supplied furnishes the oxygen which aided by the furnace h eat dissociates the hydrogen from the chlorin. The pipe 56 may have a valve, as 56 and the pipe 62 may be continued as a pipe at 62 whereby the aqueous acid from tank 60 may be slowly supplied to said pipe 56 preferably at some point beyond the valve 56.

oxygen which is thus taken from the air is held in a combination, H20, ready for be-l ing released in the required nascent state, when this H20 shall be dissociated for utilizing the oxygen in oxidizing the sulfur dioxid (SO2) into sulfur trioxid, (SU). Thus, by the dissociation in the. way indi cated, of, of the hydrochloric acid, the chlorin is regularly returned into the principal process, and to the combining apparatus in the same proportionate or measured quantity in which it is Withdrawn from the chamber M, and in which it is required in the chamber 4,-, so that the process itself, by its continuous operation, provides and reuses, continually, the same circulating supply and quantity of the chlorin, without requiring renewal except to make up for any slight loss due to leakage or other accidental causes. And in a like manner, the hydrogen may be said to be dissociated from the chlorin and to be oxidized in said apparatus 20, so that the process itself, by its continnous operation provides continually the required current of hydrogen for first joining with oxygen in the apparatus 20; next for holding the hydrogen until reaching the chamber 4f; and finally for there releasing the oxygen in a nascent state for oxidizing the sulfur dioxid, and releasing the hydrogen for re-combining with the chlorin. lllhus the complete circuit has continuously present in all parts thereof, a quantity of chlorin. accompanied by a. quantity of hydrogen, and if we consider the hydrogen as a basic element, this may be regarded as shifting to a combination with chlorin in one part of the circuit, and to a combination with oxygen in another part of the circuit, and so on, in a continuous manner.

Furthermore, the air (N and O) supplied to the dissociation apparatus 20, in connection with hydrochloric material, furnishes,-in addition to the required oxygen for' combining With the hydr0gen,-a relatively large quantity of the nitrogen for diluting the materials iiowing through said pipe 29, and for thereby through expansion and absorption of heat, modifying and controlling the temperature conditions not only in said conduit 29, but alsosubsequently thereto, during the principal process. These features in connection with the several reactions, result in a final completion of the acid-forming process in such a way as to largely balance the heat of' reaction with that which disappears by the changes in the combining and dissociating actions, so that only a, relatively small amount of surplus heat remains to be disposed of by means of the described cooling arrangements. Thus the complete process, by reason of the features here explained, involves a minimum cost for excess or waste heat, since it also provides for effecting the principal reactions under a moderate temperature instead of the high temperature which, otherwise, such a direct and intensive manufacture of the sulphuric acid might naturally produce.

By supplying to the circuit of the process a neutral gas,-as nitrogen or a mixed gas consisting mainly of nitrogen,-this gas serves as a diluent of, and also as a carriergas for the other materials, and cooperates therewith in severalways. By its diluent action, the carrier gas enlarges the total volume and accele ates the flow of the incorporated materials passing through the reaction zones of the circuit, and also by its expansion when heated, tends by the absorption of heat to favorably modify the temperature conditions throughout the process. These features of the neutral gasand of its modes of mechanical and physical action, also tend to reduce the otherwise normal violence of the principal reactions and to increase the time interval thereof. By suitably regulating the excess and proportionate quantity of the carrier gas, the actions and the reactions may be so modulated as to avoid any unduly destructive effects of the heat upon the apparatus.

In order to avoid making a dilute sulfuric acid. the quantity of water, H2O, supplied by the pipe S, must be restricted, of course, to the amount. needed for supplying the required elements for the acid-forming reactions involved in the production of the fuming acid. lVhen the steam-supply through the nozzle n is only sufficient in quantity of H2() for that purpose, and if then a greater jet-action is desired, this may be obtained by using a higher steam pressure, and thereby secure a more intense mechanical agitation of the incorporated materials in the combining spaces l and G; also the dryness, or the superheat of the steam may be regulated or increased as found desirable.

rl`he two cooperative carrier-streanis-in this instance comprising the chlorin and the hydrogen,-together constitute a two-substance oxygentransferring current which operates in the process and under the conditions thereof, to take up one proportion of oxygen from a compound gas containing oxygen, and convey the same to the sulfur dioxid, and there yield up said oxygen in a nascent state directly to the sulfur for thereby converting the dioxid into the trioxid thereof. In these actions and reactions, as will now be evident, the sulfur dioxid and a carrier-gas are mixed with a gaseous compound comprising combined therein, oxygen gas and anon-oxygen gas, and said compound is dissociated for releasing the oxygen in nascent state or form, and this nascent oxygen is combined with the sulfur dioxid to make sulfur trioxid, and, simultaneously, said non-oxygen gas is combined with the carrier-gas, said reactions and dissociation being effected under the action of water which is in the form of a flowing current of expandi1ig,-and preferably super-heated,- Steam of a quantity only sulicient for combining with a portion of the trioxid, whereby on 'condensation of the combined sulfur trioxid. and water to liquid form the remaining portion of the trioxid is incorporated or dissolved therein. By increasing the quantity of water, however, the proportion of the uncombined trioxid may be reduced, and thus make the compound product a 100% acid, or a dilute acid.

Having thus described my invention, I claim:

l. A process of continuously re-using chlorin in the manufacture of a sulfur cornpound comprising sulfuric acid and sulfur trioxid, which consists in continuedly circulating in a multiestage circuit, hydrogen and chlorin, incorporating thc hydrogen and chlorin while combined as hydrochloric acid in a mixture with oxygen and a neutral gas each supplied to the circuit at one stage thereof in a continued stream, and heating this mixture to the point of dissociating the hydrogen from the chlorin and combining this hydrogen with the oxygen t'o form a water vapor; next in a further stage of the circuit, adding .sulfur dioxid also supplied in a continued stream, and converting the sulfur dioxid into sulfur trioxid by dissociating said water vapor and combining the oxygen thereof with the sulfur dioxid while re-combining the said hydrogen thereof with the chlorin; and, sinuiltaneously with this recombining operation, incorporating the entire mixture with steam supplied in a quantity sufficient to convert only a portion of the sulfur trioxid into sulfuric acid.

2. A process of continuously re-using chlorin in the manufacture of sulfur compounds comprising sulfuric acid, which consists in continuedly circulating in a multistage circuit, hydrogen and chlorin, incorporating the hydrogen and chlorin while combined as hydrochloric acid in a mixture with oxygen and a neutral gas each supplied to the circuit at one stage thereof in a continued stream, arid heating this mixture to tho point of dissociating the hydrogen from the chlorin and combining this hydrogen with the oxygen to form a Water vapor; next in a further stage of the circuit, adding sulfur dioxid and steam each supplied 1n a continued stream, and converting the sulfur dioxid into sulfur trioxid by dissociating said Water vapor and combining the oxygen thereof with the sulfur dioxid While re-combining the said hydrogen thereof with the chlorin while the entire mixture is incorporated with the steam.

3. A process of continuously 1e-;'using -chlorin in the manufacture of sulfur compounds comprising` sulfuric acid, which consists 1n continuedly circulating 1n a circuit, hydrogen and chlorin7 incorporating tinued stream and converting the sulfur.

dioxid into sulfur trioxid by dissociating said water vapor and combining the oxygen thereof with the sulfur dioxid and recombilling the said hydrogen thereof With the chlorin While the entire mixture is incorporated with the steam.

4t. i process ot continuously re-using chlorin in the manufacture of mixed sulfuric acid and sulfur trioxid, which consists in circulating hydrogen and chlorin continuously in' closed circuit having therein three process-stages, and at one stage in the circuit incorporating together in a heated stream the chlorin content and the hydrogen while combined with chlorin, with a neutral gas and with sulfur dioxid, intermingling said incorporated materials with expanding steam supplied to said f heated stream in proportions for thereby dissociating the hydrogen from the chlorin of ,the hydrochloric acid and then continuing the re-incorporating and re-combining the elements thereof in a continuous circuit and process in which the circuit-form stream comprising the chlorin in a given quantity passes through one process-stage of the closed circuit in which the chlorin is in combination with hydrogen, and passes through another stage of the circuit in a ,mixture with the same hydrogen while this is combined with oxygen, whereby the chlorin is supplied to the combining chamber in an uncombincd form, and in the same quantity as existing in the saidi combined form thereof.

f5. A process of continuously re-using chlorin in the manufacture of mixed sulfuric acid and sulfur trioxid, which consists in circulating hydrogen and chlorin :in a closed circuit, and at one place in the circuit incorporating the uncou'lbined h vdrogen and chlorin with nitrogen and sulfur dioxid and also with water vapor and with expanding steam, supplied in proportions for thereby converting the sulfur dioxid into sulfuric acid associated with sulfur trioxid and also forming hydrochloric acid, next at another place in thc circuit separating these products and later at a third place in the circuit subjecting the hydrochloric acid to dissociation, and then to re-incorporation and re-combination as before, in a continuous circuit and process in which the circuit-form stream'comprising the chlorin in a given quantity passes through one part of the closed circuit in an acid combination with hydrogen, and through another part oi' the circuit in a mixture with the same hydrogen While this is combined with oxygen, and is thereby supplied uncombined to a combining chamber in the circuit, in the same proportions as existing in the said combined form thereof.

EDl/Vlhl D. GHAPLlN.

Witnesses:

l-li. D. PENNEY,

l-I. li. Smeer.. 

